Process for rendering textile materials water-repellent



Patented Juiy 7, 1942 PROCESS FOR RENDERING TEXTILE MATERIALS WATER-REPELLENT Ernst Waltmann, Krefeld, Germany, assignor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application April 11, 1939, ,Serial .4 Claims.

This inventionrelates to treating textile materials and particularly to rendering them waterrepellent and to products obtained thereby.-

This application is a continuation in part of my co-pending application Serial No. 182,915 filed December 31, 1937.

In Germany January 2, 1937 I have found in accordance with my invention that for the purpose of preparing fibers for dyeing, I may treat them with an ether containing a basic nitrogen atom. Such treatment in the case ofcotton or other cellulosic material is capable of animalizing the material, that is of imparting to it characteristics of animal fibers, such as wool, whereby the material so treated can be dyed with acid dyes. In addition I have found in accordance with my invention that where the compounds employed for treatment are of a higher molecular weight there is imparted to the fibers, whether they be of cellulose containing material, wool or other material having similar properties, a permanent power of resistance to wetting by water. That is, the fibers have a water-repellence which resists ordinary house laundering and dry cleaning. In the case of cellulose-containing fibers, such as cotton, viscose. and other artificial silks in addition to the water-repellence, the above mentioned animalizing of the fiber occurs.

Processes have been alrady proposed for introducing into viscose solution an addition of casein. albumen or other nitrogenous substances, and it has also been proposed to treat alkali or alkaline earth compounds of cellulose with alkalizing nitrogenous agents. These proposed processes, however, are either expensive or do not produce a uniform result in the fibers treated and are not practical for large scale production.

An important object of my invention'accordin this radical at least one basic nitrogen atom.

.The compounds can be brought into water soluble condition in the form of their quaternary ammonium compounds so that the entire treatment is carried out in an aqueous solution. If

.the compounds contain aliphatic, aliphaticaromatic or alicyclic radicals having at least ten carbon atoms in a straight chain, there is imparted to the fibers a permanent power of resistance. to wetting with water.

, Fibers of cellulosic material which have been treated in accordance with my invention are well suited to mixture with wool fibers. The mixed fabrics manufactured therefrom can be dyed in the usual manner with dyes which incline to acidity, whereby a considerable saving in dye is attained, as well as saving in the dyeingprocess.

The invention accordingly comprises impregnating textile material with the reaction product of a cyanhydrin, formaldehyde, 9. hydrohalic acid and a tertiary amine, containing an aliphatic radical of at least ten carbon atoms and baking the dried impregnated material to produce waterrepellence therein.

The following are examples of embodiments of the manner in which I now prefer to practice the invention in the treatment of textiles. It is to be understood that the invention is not limited thereto except as indicated in the appended claims.

Examples 1. Undyed, unbrightened loose spun rayon flock is introduced into an aqueous bath heated to about 40 C. containing per liter 15 grams of the quaternary pyridinium salt of the methyl chloride compound prepared from octadecane cyanhydrine CH3(CI-I2)1c.CH(OH)CN, trioxymethylene and hydrochloric acid gas as described hereinafter. The bath also cont-tins besides per liter 5 grams of sodium acetate. After impregnation the material is centrifuged, dried and exposed for about 6 hours to a temperature of about 100 C. The spun rayon which has been treated in this way shows a wat'er-repellence which resists washing with soap and water and also resists dry-cleaning by benzine. In the presence of soap or other wetting agents the water-repellent material so produced may be dyed hot. The dyeing bath contains per liter: 1 part of benzene light blue FR, (Schultz-Julius Farbstofitabellen 1931, No. 617)' 10 parts of sodium sulphate, 0.5 part of soap-V. In the dyeing bath thus obtained 50 parts of loose spun rayon flock are dyed for 1 hour at -90 C. After thorough rinsing of the wetting agent or soap the water-repellent effect reappears.

2. A dyed dress material of mercerized cotton is treated in an aqueous solution of 20 grams per liter of the quaternarypyridinium salt of the aqueous bath as described in Example 1.

impregnation the material is squeezed out and "dried at a temperature of about 60 C. After drying the material is heated for 20 minutes to a -temperature of about 130 C. The water-repelmethyl chloride compound results.

methyl chloride compound prepared from dodecane cyanhydrlne CH3(CH2)10CH(OH).CN trioxymethylene and hydrochloric acid gas as described hereinafter. The bath also contains besides per liter 5 grams of sodium acetate. After impregnation the material is squeezed out and dried at a temperature of about 60 C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber. The treated material shows water-repellence which is proof against dry-cleaning and washing with soap.

3. A printed crepe consisting of real silk in warp and weft is treated in an aqueous solution of grams per liter of the quaternary pyridinium salt of themethyl chloride compound prepared from octadecane cyanhydr'me CH3 (CH2) 16CH (OH) .CN

drine CH3. (CH2) 1o.CH (OH) CN trioxymethylene' and hydrochloric acid gas as described hereinafter. The bath also contains 5 grams per liter f of sodium acetate; After impregnation the mavj f terial is squeezed out and dried at a temperature "of about 60 C. and after drying is heated for an hour to a temperature of 110 C. The water-ref'pellent effect is like that of Example 2.

,5. -A mixed fabric consisting of viscose rayon in warp and cotton crepe in weft is treated in an After lent effect is like that of Example 2.

The result of the treatment of the textiles in the manner. above'described is to cause an action between the textile and the treatingagent, producing water repellence.

Dyeing with acid dyes may be carried out, particularly on the cellulosic material, treated in accordance with, the above examples, if desired.

The following are processes for producing chemicals mentioned above:

"6. The methyl chloride compounds are first ylene until the formation of the methyl chloride compound is completed, Whichcan be clearly recognized by the carbon tetrachloride solution be-.

coming clear. The water from the reaction- I which accumulates at the bottom of the vessel is 1 runoff; the carbon tetrachloride and the surplus hydrochloric acid are removed in a vacuum. The

quaternary ammonium salt of the methyl. chloride compound for example with pyridine is formed in the following manner: 360 parts of the methyl chloride compound are stirred with 80 parts of pyridine. The mixture solidifies immediately and the quaternary pyridinium salt of the To remove impurities the salt is washed with acetone. The probable formula of the compound is as follows: CIla(CHz)nCH(0H).C:(NH)00E, 01

7. Dry hydrochloric acid gas is introduced at ordinary temperature into a mixture containing 202 parts of dodecane cyanhydrine, 800 parts of carbon tetrachloride, parts of trioxymethylene until the formation of the methyl chloride compound is completed which can be clearly recognized by the carbon tetrachloride solution becoming clear. The water from the reaction which accumulates at thebottom of the vessel is run off; the carbon tetrachloride and the surplus hydrochloric acid are removed in a vacuum.

The quaternary ammonium salt with pyridine is formed in the following manner: 276 parts of the methyl chloride compound are stirred with parts of pyridine. The mixture solidifies immediately. The formed quaternary pyridine salt is washed with acetone to remove impurities. The probable formula of the compound is as follows:

CH3.(CH2)10.CH(OH).C:(NH)00g:

In the above examples other tertiary amines may be employed such as trimethylamine, etc. to replace pyridine for the production of water soluble compounds.

The processes of the invention, particularly as set forth in the specific embodiments, may be carried out with simple apparatus at relatively small expense and in arelatively short time.

The textile products show an improved appear- I ance, their feel as compared with similar untreated material is not substantially altered, their dyeing properties are altered, and where the higher carbon compounds are used, they have -a high degree of water-repellence which does not rapidly disappear upon cleansing by laundering or otherwise of the materials produced.

'The term textile material as herein employed is intended to include fibers, yarns, fabrics or other forms of wool and silk as well as cellulosic material. The expression cellulosic-material as herein employed is intended to cover fibers, yarns, fabrics or other forms of cotton, jute, linen, hemp or rayon including viscose, cuprammonium, or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose, so long as such materials still contain a hydroxyl group or groups that will act with the agents herein employed to produce the dyeing effects and/or water-repellent effects herein described.

Other forms of formaldehyde instead of trioxymethylene may be used, and substances splitting formaldehyde under the reaction conditions for the manufacture of the chemical substances herein may also be employed.

The expression hydrohalic acid as employed in the claims is intended .to cover not only hydrochloric acid herein specifically given as part of the preferred form of my invention, but, as well, similar acids containing other halogens than chlorine and having the same general properties' as the preferred acid for the purpose stated.

which comprises impregnating textile 7' While the invention has been described in detail according to the preferred manner of carrying out the process, it will be obvious to those skilledin the art after understanding the invention, that changes and modifications may be made therein without departing from the spirit or scope of the invention and it is intended in the appended claims to cover all such changes and modifications.

What is claimed as new and desired to be secured by Letters Patent is: v

1. A process for modifying textile material material with the reaction product of a cycanhydrin, trioxymethylene, a hydrohalic acid, and a'tertiary l5 amine, said product containing an aliphatic radical of at least ten carbon atoms, and heatmg the dried impregnated material to produce water-repellenee therein.

above about 100 C.

3. A process for modifying textile material which comprises impregnating the material with the reaction product of octadecane cyanhydrin,

trioxyniethy'lene, hydrochloric acid and pyri-v dine, and baking the dried impregnated material to produce water-repellence therein.

4. A process according to claim 1 in which the textile material treated is cellulosic material and the heating is carried on at a temperature ERNST WAL'IMANN. 

